CN104923237A - Phenol ortho-position methylation catalyst and preparation method therefor as well as method for catalytically synthesizing phenol ortho-position methylation compound by using phenol ortho-position methylation catalyst - Google Patents
Phenol ortho-position methylation catalyst and preparation method therefor as well as method for catalytically synthesizing phenol ortho-position methylation compound by using phenol ortho-position methylation catalyst Download PDFInfo
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- CN104923237A CN104923237A CN201510239694.9A CN201510239694A CN104923237A CN 104923237 A CN104923237 A CN 104923237A CN 201510239694 A CN201510239694 A CN 201510239694A CN 104923237 A CN104923237 A CN 104923237A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention provides a phenol ortho-position methylation catalyst which comprises a compound oxide catalyst containing ferrum, silicon, magnesium, cerium and potassium. In the compound oxide catalyst, the molar ratio of ferrum, silicon, magnesium, cerium and potassium is 1: (0.01-0.05): (0.01-0.05): (0.01-0.05): (0.01-0.05). In addition, the invention further provides a preparation method of the phenol ortho-position methylation catalyst as well as a method for catalytically synthesizing a phenol ortho-position methylation compound by using the phenol ortho-position methylation catalyst. The phenol ortho-position methylation catalyst has microstructures of 10 nm to 100 nm, can bear the mass space velocity being greater than 1.5/h, and is long in service life, free of heavy metals and green and environmental-friendly. According to the phenol ortho-position methylation compound which is catalytically synthesized by the catalyst, the product is few in purity and less in wastewater, the conversion rate of phenol is not changed at the mass space velocity being greater than 1.5/h, and the selectivity of the phenol ortho-position methylation compound is improved.
Description
Technical field
The present invention relates to alkylation of phenol catalyst, particularly relate to a kind of phenol ortho-methylation catalyst, its preparation method and utilize the method for the ortho-methylated compound of its synthesizing phenol.
Background technology
Orthoresol is a kind of important organic chemical industry's intermediate for the synthesis of agricultural chemicals, dyestuff, spices and antioxidant etc.; 2,6-xylenol is a kind of important organic chemical industry's intermediate for the synthesis of agricultural chemicals such as polyphenylene oxide engineering plastics (PPO) and metalaxyl, furalaxyl, ofurace, fenfuram, delachlor and dimethachlors.
Traditional orthoresol and 2,6-xylenol adopt the preparation of phenol methanol vapor phase alkylation process, and its catalyst generally used is generally MgO, Al
2o
3and Fe
2o
3.The temperature required height of MgO catalyst reaction (> 450 DEG C), Al
2o
3catalyst Production product complex distribution, target product selective low, not easily separated, therefore Fe
2o
3catalyst becomes the hot topic of research at present.
But traditional Fe
2o
3there is following shortcoming in catalyst: such as Fe/Mg/ heteropolyacid catalyst, heteropoly acid easily runs off instability, and catalyst can not bear high-speed, Fe/Mg/Sb catalyst is then because Sb is wherein heavy metal, do not meet the requirement of green chemical industry, the transition metal such as Fe/Mg/M(M=Ce, Zn, Mn, Cu) catalyst then the life-span short, can not for the production of 2,6-xylenol.
Summary of the invention
Based on this, be necessary for traditional Fe
2o
3it is short and do not meet the problem of green chemical industry that catalyst can not bear high-speed, life-span, provides a kind of phenol ortho-methylation catalyst that can bear the long and environmental protection of high-speed, life-span.
The present invention also provides a kind of preparation method of phenol ortho-methylation catalyst.
In addition, the present invention also provides a kind of method utilizing the ortho-methylated compound of above-mentioned catalyst synthesizing phenol.
A kind of phenol ortho-methylation catalyst, this catalyst is the composite oxide catalysts containing iron, silicon, magnesium, cerium, potassium, in above-mentioned composite oxide catalysts, the mol ratio between iron, silicon, magnesium, cerium, potassium is 1:0.01 ~ 0.05:0.01 ~ 0.05:0.01 ~ 0.05:0.01 ~ 0.05.
A preparation method for phenol ortho-methylation catalyst, comprises the following steps:
Soluble ferric iron salt, silicon-containing compound, solubility magnesium salts, solubility cerium salt and soluble potassium salt are mixed, obtain the first solution, in above-mentioned first solution, the mol ratio between iron, silicon, magnesium, cerium, potassium is 1:0.01 ~ 0.05:0.01 ~ 0.05:0.01 ~ 0.05:0.01 ~ 0.05;
By polyethylene glycol and ammoniacal liquor mixing, obtain the second solution, in above-mentioned ammoniacal liquor, the molal quantity of ammonia is 5 ~ 10 times of the molal quantity of iron in above-mentioned soluble ferric iron salt, and the quality of above-mentioned polyethylene glycol is 5% ~ 25% of catalyst quality;
Under ul-trasonic irradiation, by above-mentioned first solution and the mixing of the second solution, stir, obtain mixed liquor;
Above-mentioned mixed liquor is filtered, obtains filter cake; And
By above-mentioned Washing of Filter Cake, drying, roasting, obtain catalyst, this catalyst is the composite oxide catalysts containing iron, silicon, magnesium, cerium, potassium, in above-mentioned composite oxide catalysts, the mol ratio between iron, silicon, magnesium, cerium, potassium is 1:0.01 ~ 0.05:0.01 ~ 0.05:0.01 ~ 0.05:0.01 ~ 0.05.
Wherein in an embodiment, above-mentioned soluble ferric iron salt is iron chloride, ferric nitrate or ferric sulfate; Above-mentioned silicon-containing compound is Ludox, silica or positive silicic acid; Above-mentioned solubility magnesium salts is magnesium chloride, magnesium nitrate or magnesium sulfate; Above-mentioned solubility cerium salt is cerous nitrate, cerium chloride or cerous sulfate; Above-mentioned soluble potassium salt is potassium chloride, potassium nitrate or potassium sulfate.
Wherein in an embodiment, above-mentioned hyperacoustic vibration frequency is: 20kHz.
Wherein in an embodiment, by the step of above-mentioned Washing of Filter Cake, the method for this washing is specially: first wash with water and wash with ethanol.
Wherein in an embodiment, above-mentioned under hyperacoustic effect, in the step above-mentioned first solution and the second solution are mixed, stirred, the time of this stirring is 0.5 ~ 5 hour.
Wherein in an embodiment, the method for above-mentioned drying is specially: at 100 DEG C ~ 180 DEG C microwave dryings.
Wherein in an embodiment, the condition of above-mentioned roasting was specially: 550 DEG C ~ 650 DEG C roastings 15 ~ 25 hours.
Wherein in an embodiment, by above-mentioned Washing of Filter Cake, drying, roasting, further comprising the steps of after obtaining the step of catalyst:
By compressing tablet after above-mentioned catalyst porphyrize.
Utilize phenol ortho-methylation catalyst to catalyze and synthesize a method for phenol ortho-methylation compound, comprise the following steps:
Mix after the gasification of the mixed solution of phenol, first alcohol and water with carrier gas, under the effect of catalyst, carry out vapor phase alkylation, obtain phenol ortho-methylation compound, this catalyst is the composite oxide catalysts containing iron, silicon, magnesium, cerium, potassium, in above-mentioned composite oxide catalysts, the mol ratio between iron, silicon, magnesium, cerium, potassium is 1:0.01 ~ 0.05:0.01 ~ 0.05:0.01 ~ 0.05:0.01 ~ 0.05.
Above-mentioned phenol ortho-methylation catalyst has the microstructure of 10nm ~ 100nm, can bear 1.5h
-1above mass space velocity, life-span are grown and do not contain heavy metal, environmental protection.
In addition, the above-mentioned phenol ortho-methylation compound utilizing phenol ortho-methylation catalyst to catalyze and synthesize, product impurity is few, waste water is few, at 1.5h
-1under above mass space velocity, the conversion ratio of phenol is constant, the selective raising of phenol ortho-methylation compound.
Accompanying drawing explanation
Fig. 1 is preparation method's schematic flow sheet of the phenol ortho-methylation catalyst of an embodiment.
Fig. 2 is the micro-structure diagram of catalyst prepared by embodiment 1.
Fig. 3 is the micro-structure diagram of catalyst prepared by embodiment 2.
Fig. 4 is the micro-structure diagram of catalyst prepared by embodiment 3.
Fig. 5 is the micro-structure diagram of catalyst prepared by embodiment 4.
Fig. 6 is the micro-structure diagram of catalyst prepared by comparative example 1.
Detailed description of the invention
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail the specific embodiment of the present invention below in conjunction with accompanying drawing.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar improvement when intension of the present invention, therefore the present invention is by the restriction of following public concrete enforcement.
A kind of phenol ortho-methylation catalysis, this catalyst is the composite oxide catalysts containing iron, silicon, magnesium, cerium, potassium.
Wherein, in this composite oxide catalysts, the mol ratio between iron (Fe), silicon (Si), magnesium (Mg), cerium (Ce), potassium (K) is 1:0.01 ~ 0.05:0.01 ~ 0.05:0.01 ~ 0.05:0.01 ~ 0.05.
Refer to Fig. 1, be the preparation method of the phenol ortho-methylation catalyst of an embodiment, comprise the following steps:
S110, by soluble ferric iron salt, silicon-containing compound, solubility magnesium salts, solubility cerium salt and soluble potassium salt mix, obtain the first solution.
Wherein, in the first solution, the mol ratio between iron, silicon, magnesium, cerium, potassium is 1:0.01 ~ 0.05:0.01 ~ 0.05:0.01 ~ 0.05:0.01 ~ 0.05;
In the present embodiment, soluble ferric iron salt is iron chloride (FeCl
3), ferric nitrate (Fe (NO
3)
3) or ferric sulfate (Fe
2(SO
4)
3).Silicon-containing compound is Ludox, silica (SiO
2) or positive silicic acid.Solubility magnesium salts is magnesium chloride (MgCl
2), magnesium nitrate (Mg (NO
3)
2) or magnesium sulfate (MgSO
4).Solubility cerium salt is cerous nitrate (Ce (NO
3)
3), cerium chloride (CeCl
3) or cerous sulfate (Ce
2(SO
4)
3).Soluble potassium salt is potassium chloride (KCl), potassium nitrate (KNO
3) or potassium sulfate (K
2sO
4).
S120, by polyethylene glycol and ammoniacal liquor mixing, obtain the second solution.
Wherein, the quality of polyethylene glycol is 5% ~ 25% of catalyst quality.
In ammoniacal liquor, the molal quantity of ammonia is 5 ~ 10 times of the molal quantity of iron in soluble ferric iron salt.
Be appreciated that step S110 and step S120 order in no particular order, as long as the first solution and the second solution are ready to.
S130, under ul-trasonic irradiation, by above-mentioned first solution and the second solution mixing, stir, obtain mixed liquor.
Wherein, hyperacoustic vibration frequency is: 20kHz.
In the step above-mentioned first solution and the second solution are mixed, stirred, the method for mixing is specially: above-mentioned first solution and the second solution are mixed in the mode also flowed.
In the present embodiment, the time of stirring is 0.5 ~ 5 hour.Preferably, the time of stirring is 2 hours.
S140, above-mentioned mixed liquor to be filtered, obtain filter cake.
S150, by above-mentioned Washing of Filter Cake, drying, roasting, obtain catalyst.
Wherein, catalyst is the composite oxide catalysts containing iron, silicon, magnesium, cerium, potassium.In this composite oxide catalysts, the mol ratio between iron, silicon, magnesium, cerium, potassium is 1:0.01 ~ 0.05:0.01 ~ 0.05:0.01 ~ 0.05:0.01 ~ 0.05.
In the present embodiment, the method for washing is specially: first wash with water and wash with ethanol.
Preferably, first wash 5 times with water, then with ethanol washing, water is cemented out.
Dry method is specially: at 100 DEG C ~ 180 DEG C microwave dryings.The condition of roasting was specially: 550 DEG C ~ 650 DEG C roastings 15 ~ 25 hours.Preferably, 600 DEG C of roastings 20 hours.
In the present embodiment, the preparation method of above-mentioned phenol ortho-methylation catalyst, further comprising the steps of after step s 150:
By compressing tablet after above-mentioned catalyst porphyrize.
Concrete, the condition of above-mentioned compressing tablet is: 30kg forming under the pressure 5mm × 3mm circular granular sheet.
Above-mentioned phenol ortho-methylation catalyst has the microstructure of 10nm ~ 100nm, can bear 1.5h
-1above mass space velocity, run 2000 hours catalyst and still have excellent activity, the life-span is long, and not containing heavy metal, environmental protection.
Utilize phenol ortho-methylation catalyst to catalyze and synthesize a method for phenol ortho-methylation compound, comprise the following steps:
Mix after the gasification of the mixed solution of phenol, first alcohol and water with carrier gas, under the effect of catalyst, carry out vapor phase alkylation, obtain phenol ortho-methylation compound.
Wherein, catalyst is the composite oxide catalysts containing iron, silicon, magnesium, cerium, potassium.In this composite oxide catalysts, the mol ratio between iron, silicon, magnesium, cerium, potassium is 1:0.01 ~ 0.05:0.01 ~ 0.05:0.01 ~ 0.05:0.01 ~ 0.05.
In the present embodiment, carrier gas is nitrogen, and carrier gas flux is 25ml/min.
It is below specific embodiment.
embodiment 1
1mol ferric nitrate, 0.01mol Ludox, 0.01mol magnesium nitrate, 0.01mol cerous nitrate and 0.01mol potassium nitrate are mixed, obtains the first solution.
By 2g polyethylene glycol and the mixing of 200ml ammoniacal liquor, obtain the second solution.Wherein, the quality of polyethylene glycol is 5% of catalyst quality, and in ammoniacal liquor, ammonia is 5mol.
Under ul-trasonic irradiation, by above-mentioned first solution and the mixing of the second solution, stir 2 hours, obtain mixed liquor.This mixed liquor is filtered, obtains filter cake.After filter cake being washed with water 5 times, cemented out by water with ethanol washing, then microwave drying, 600 DEG C of roastings 20 hours, obtain catalyst, this catalyst can be expressed as: FeSi
0.01mg
0.01ce
0.01k
0.01.
By above-mentioned catalyst porphyrize, compressing tablet, TEM shows the micro-structure diagram that this catalyst has 10nm ~ 100nm as shown in Figure 2.
Catalyst Fe Si prepared by embodiment 1
0.01mg
0.01ce
0.01k
0.01for catalyzing and synthesizing orthoresol: mix after the gasification of the mixed solution of 1mol phenol, 3mol methyl alcohol and 1mol water with carrier gas, under the effect of this catalyst, carry out vapor phase alkylation, wherein, reaction temperature is 320 DEG C, and normal pressure, mass space velocity are 3.0h
-1, flow rate of carrier gas is 25mL/min, catalyst one way stable operation 2000 hours, and phenol average conversion is 50.51%, and orthoresol average selectivity is 90.08%.
Catalyst Fe Si prepared by embodiment 1
0.01mg
0.01ce
0.01k
0.01for catalyzing and synthesizing 2,6-xylenol: mix after the gasification of the mixed solution of 1mol phenol, 5mol methyl alcohol and 1mol water with carrier gas, under the effect of this catalyst, carry out vapor phase alkylation, wherein, reaction temperature is 350 DEG C, and normal pressure, mass space velocity are 1.0h
-1, flow rate of carrier gas is 25mL/min, catalyst one way stable operation 2000 hours, and phenol average conversion is 99.90%, 2,6-xylenol average selectivity is 98.23%.
Comparative example 1
1mol ferric nitrate, 0.01mol Ludox, 0.01mol magnesium nitrate, 0.01mol cerous nitrate and 0.01mol potassium nitrate are mixed, obtains the first solution.
By 8g polyethylene glycol and the mixing of 200ml ammoniacal liquor, obtain the second solution.Wherein, the quality of poly-adopted glycol is 5% of catalyst quality, and in ammoniacal liquor, ammonia is 5mol.
Under ul-trasonic irradiation, by above-mentioned first solution and the mixing of the second solution, stir 2 hours, obtain mixed liquor.This mixed liquor is filtered, obtains filter cake.After filter cake being washed with water 5 times, cemented out by water with ethanol washing, then 100 DEG C of oven dryings, 600 DEG C of roastings 20 hours, obtain the catalyst of comparative example 1.
By catalyst porphyrize, the compressing tablet of comparative example 1, TEM shows this catalyst and has micro-structure diagram as shown in Figure 6.
As can be seen from Fig. 2 and Fig. 6, use the grain size of the catalyst of oven drying to be greater than the catalyst using microwave drying, illustrate that the catalyst dispersion effect of microwave drying is better than the catalyst of oven drying.
The catalyst of embodiment 1 sees the following form with the physical arrangement of the catalyst of comparative example 1 and comparing of catalytic performance.
The comparison of catalyst prepared by table 1 microwave method and oven method
Condition: phenol: methyl alcohol: water=1:5:1; Reaction temperature 320 DEG C-350 DEG C; Mass space velocity:
3.0 h
-1; Pressure: normal pressure; Nitrogen stream: 10 mLmin
As can be seen from Table 1: use the specific area of the catalyst of microwave drying, pore volume and catalytic activity to be all greater than the catalyst using oven drying.
embodiment 2
1mol ferric nitrate, 0.05mol Ludox, 0.05mol magnesium nitrate, 0.05mol cerous nitrate and 0.05mol potassium nitrate are mixed, obtains the first solution.
By 40g polyethylene glycol and the mixing of 200ml ammoniacal liquor, obtain the second solution.Wherein, the quality of poly-adopted glycol is 25% of catalyst quality, and in ammoniacal liquor, ammonia is 10mol.
Under ul-trasonic irradiation, by above-mentioned first solution and the mixing of the second solution, stir 2 hours, obtain mixed liquor.This mixed liquor is filtered, obtains filter cake.After filter cake being washed with water 5 times, cemented out by water with ethanol washing, then microwave drying, 650 DEG C of roastings 25 hours, obtain catalyst, this catalyst can be expressed as: FeSi
0.05mg
0.05ce
0.05k
0.05.
By above-mentioned catalyst porphyrize, compressing tablet, TEM shows the micro-structure diagram that this catalyst has 10nm ~ 100nm as shown in Figure 3.
Catalyst Fe Si prepared by embodiment 2
0.05mg
0.05ce
0.01k
0.05for catalyzing and synthesizing orthoresol: mix after the gasification of the mixed solution of 1mol phenol, 3mol methyl alcohol and 1mol water with carrier gas, under the effect of this catalyst, carry out vapor phase alkylation, wherein, reaction temperature is 320 DEG C, and normal pressure, mass space velocity are 3.0h
-1, flow rate of carrier gas is 25mL/min, catalyst one way stable operation 2000 hours, and phenol average conversion is 45.56%, and orthoresol average selectivity is 93.08%.
Catalyst Fe Si prepared by embodiment 2
0.05mg
0.05ce
0.05k
0.05for catalyzing and synthesizing 2,6-xylenol: mix after the gasification of the mixed solution of 1mol phenol, 5mol methyl alcohol and 1mol water with carrier gas, under the effect of this catalyst, carry out vapor phase alkylation, wherein, reaction temperature is 350 DEG C, and normal pressure, mass space velocity are 1.2h
-1, flow rate of carrier gas is 25mL/min, catalyst one way stable operation 2000 hours, and phenol average conversion is 99.93%, 2,6-xylenol average selectivity is 88.00%.
embodiment 3
1mol ferric nitrate, 0.01mol Ludox, 0.01mol magnesium nitrate, 0.01mol cerous nitrate and 0.01mol potassium nitrate are mixed, obtains the first solution.
By 8g polyethylene glycol and the mixing of 200ml ammoniacal liquor, obtain the second solution.Wherein, the quality of poly-adopted glycol is 5% of catalyst quality, and in ammoniacal liquor, ammonia is 5mol.
Under ul-trasonic irradiation, by above-mentioned first solution and the mixing of the second solution, stir 2 hours, obtain mixed liquor.This mixed liquor is filtered, obtains filter cake.After filter cake being washed with water 5 times, cemented out by water with ethanol washing, then microwave drying, 550 DEG C of roastings 15 hours, obtain catalyst, this catalyst can be expressed as: FeSi
0.01mg
0.01ce
0.01k
0.01.
By above-mentioned catalyst porphyrize, compressing tablet, TEM shows the micro-structure diagram that this catalyst has 10nm ~ 100nm as shown in Figure 4.
Catalyst Fe Si prepared by embodiment 3
0.01mg
0.01ce
0.01k
0.01for catalyzing and synthesizing orthoresol: mix after the gasification of the mixed solution of 1mol phenol, 3mol methyl alcohol and 1mol water with carrier gas, under the effect of this catalyst, carry out vapor phase alkylation, wherein, reaction temperature is 320 DEG C, and normal pressure, mass space velocity are 3.0h
-1, flow rate of carrier gas is 25mL/min, catalyst one way stable operation 2000 hours, and phenol average conversion is 47.5%, and orthoresol average selectivity is 91.08%.
Catalyst Fe Si prepared by embodiment 3
0.01mg
0.01ce
0.01k
0.01for catalyzing and synthesizing 2,6-xylenol: mix after the gasification of the mixed solution of 1mol phenol, 5mol methyl alcohol and 1mol water with carrier gas, under the effect of this catalyst, carry out vapor phase alkylation, wherein, reaction temperature is 350 DEG C, and normal pressure, mass space velocity are 1.20h
-1, flow rate of carrier gas is 25mL/min, catalyst one way stable operation 2000 hours, and phenol average conversion is 99.90%, 2,6-xylenol average selectivity is 97.27%.
embodiment 4
1mol ferric nitrate, 0.05mol Ludox, 0.05mol magnesium nitrate, 0.05mol cerous nitrate and 0.05mol potassium nitrate are mixed, obtains the first solution.
By 8 polyethylene glycol and the mixing of 200ml ammoniacal liquor, obtain the second solution.Wherein, the quality of poly-adopted glycol is 5% of catalyst quality, and in ammoniacal liquor, ammonia is 5mol.
Under ul-trasonic irradiation, by above-mentioned first solution and the mixing of the second solution, stir 2 hours, obtain mixed liquor.This mixed liquor is filtered, obtains filter cake.After filter cake being washed with water 5 times, cemented out by water with ethanol washing, then microwave drying, 600 DEG C of roastings 20 hours, obtain catalyst, this catalyst can be expressed as: FeSi
0.05mg
0.05ce
0.05k
0.05.
By above-mentioned catalyst porphyrize, compressing tablet, TEM shows the micro-structure diagram that this catalyst has 10nm ~ 100nm as shown in Figure 5.
Catalyst Fe Si prepared by embodiment 4
0.05mg
0.05ce
0.05k
0.05for catalyzing and synthesizing orthoresol: mix after the gasification of the mixed solution of 1mol phenol, 3mol methyl alcohol and 1mol water with carrier gas, under the effect of this catalyst, carry out vapor phase alkylation, wherein, reaction temperature is 320 DEG C, and normal pressure, mass space velocity are 3.0h
-1, flow rate of carrier gas is 25mL/min, catalyst one way stable operation 2000 hours, and phenol average conversion is 45.1%, and orthoresol average selectivity is 93.08%.
Catalyst Fe Si prepared by embodiment 4
0.01mg
0.01ce
0.01k
0.01for catalyzing and synthesizing 2,6-xylenol: mix after the gasification of the mixed solution of 1mol phenol, 5mol methyl alcohol and 1mol water with carrier gas, under the effect of this catalyst, carry out vapor phase alkylation, wherein, reaction temperature is 350 DEG C, and normal pressure, mass space velocity are 1.2h
-1, flow rate of carrier gas is 25mL/min, catalyst one way stable operation 2000 hours, and phenol average conversion is 99.94%, 2,6-xylenol average selectivity is 95.5%.
Catalyst Fe Si prepared by embodiment 4
0.01mg
0.01ce
0.01k
0.01for catalysis orthoresol and the coproduction of 2,6-xylenol: mix with carrier gas, under the effect of this catalyst after the mixed solution of 1mol phenol, 3mol methyl alcohol and 1mol water is gasified, carry out vapor phase alkylation, wherein, reaction temperature is 350 DEG C, and normal pressure, mass space velocity are 1.2h
-1, flow rate of carrier gas is 25mL/min, catalyst one way stable operation 2000 hours, and phenol average conversion is 90.3%, and orthoresol average selectivity is 47.13%, 2,6-xylenol average selectivity is 52.35%.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a phenol ortho-methylation catalyst, it is characterized in that, described catalyst is the composite oxide catalysts containing iron, silicon, magnesium, cerium, potassium, in described composite oxide catalysts, the mol ratio between iron, silicon, magnesium, cerium, potassium is 1:0.01 ~ 0.05:0.01 ~ 0.05:0.01 ~ 0.05:0.01 ~ 0.05.
2. a preparation method for phenol ortho-methylation catalyst, is characterized in that, comprises the following steps:
Soluble ferric iron salt, silicon-containing compound, solubility magnesium salts, solubility cerium salt and soluble potassium salt are mixed, obtain the first solution, in described first solution, the mol ratio between iron, silicon, magnesium, cerium, potassium is 1:0.01 ~ 0.05:0.01 ~ 0.05:0.01 ~ 0.05:0.01 ~ 0.05;
By polyethylene glycol and ammoniacal liquor mixing, obtain the second solution, in described ammoniacal liquor, the molal quantity of ammonia is 5 ~ 10 times of the molal quantity of iron in described soluble ferric iron salt, and the quality of described polyethylene glycol is 5% ~ 25% of described catalyst quality;
Under ul-trasonic irradiation, by described first solution and the mixing of the second solution, stir, obtain mixed liquor;
Described mixed liquor is filtered, obtains filter cake; And
By described Washing of Filter Cake, drying, roasting, obtain catalyst, described catalyst is the composite oxide catalysts containing iron, silicon, magnesium, cerium, potassium, in described composite oxide catalysts, the mol ratio between iron, silicon, magnesium, cerium, potassium is 1:0.01 ~ 0.05:0.01 ~ 0.05:0.01 ~ 0.05:0.01 ~ 0.05.
3. the preparation method of phenol ortho-methylation catalyst according to claim 2, is characterized in that, described soluble ferric iron salt is iron chloride, ferric nitrate or ferric sulfate; Described silicon-containing compound is Ludox, silica or positive silicic acid; Described solubility magnesium salts is magnesium chloride, magnesium nitrate or magnesium sulfate; Described solubility cerium salt is cerous nitrate, cerium chloride or cerous sulfate; Described soluble potassium salt is potassium chloride, potassium nitrate or potassium sulfate.
4. the preparation method of phenol ortho-methylation catalyst according to claim 2, is characterized in that, described hyperacoustic vibration frequency is: 20kHz.
5. the preparation method of phenol ortho-methylation catalyst according to claim 2, is characterized in that, described under ul-trasonic irradiation, and in the step described first solution and the second solution are mixed, stirred, the time of described stirring is 0.5 ~ 5 hour.
6. the preparation method of phenol ortho-methylation catalyst according to claim 2, is characterized in that, by the step of described Washing of Filter Cake, the method for described washing is specially: first wash with water and wash with ethanol.
7. the preparation method of phenol ortho-methylation catalyst according to claim 2, is characterized in that, the method for described drying is specially: at 100 DEG C ~ 180 DEG C microwave dryings.
8. the preparation method of phenol ortho-methylation catalyst according to claim 2, is characterized in that, the condition of described roasting is specially: 550 DEG C ~ 650 DEG C roastings 15 ~ 25 hours.
9. the preparation method of phenol ortho-methylation catalyst according to claim 2, is characterized in that, by described Washing of Filter Cake, drying, roasting, further comprising the steps of after obtaining the step of catalyst:
By compressing tablet after described catalyst porphyrize.
10. utilize phenol ortho-methylation catalyst to catalyze and synthesize a method for phenol ortho-methylation compound, it is characterized in that, comprise the following steps:
Mix after the gasification of the mixed solution of phenol, first alcohol and water with carrier gas, under the effect of catalyst, carry out vapor phase alkylation, obtain phenol ortho-methylation compound, described catalyst is the composite oxide catalysts containing iron, silicon, magnesium, cerium, potassium, in described composite oxide catalysts, the mol ratio between iron, silicon, magnesium, cerium, potassium is 1:0.01 ~ 0.05:0.01 ~ 0.05:0.01 ~ 0.05:0.01 ~ 0.05.
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Cited By (3)
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|---|---|---|---|---|
| CN109721473A (en) * | 2017-10-30 | 2019-05-07 | 中国石油化工股份有限公司 | A method of preparing o-cresol |
| CN109833878A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of alkylation of phenol catalyst and its synthetic method of production and 2,6- xylenol |
| CN113304743A (en) * | 2021-05-14 | 2021-08-27 | 安徽海华科技集团有限公司 | Method for preparing high-purity carvacrol by using o-cresol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109721473A (en) * | 2017-10-30 | 2019-05-07 | 中国石油化工股份有限公司 | A method of preparing o-cresol |
| CN109721473B (en) * | 2017-10-30 | 2022-02-08 | 中国石油化工股份有限公司 | Method for preparing o-cresol |
| CN109833878A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of alkylation of phenol catalyst and its synthetic method of production and 2,6- xylenol |
| CN113304743A (en) * | 2021-05-14 | 2021-08-27 | 安徽海华科技集团有限公司 | Method for preparing high-purity carvacrol by using o-cresol |
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